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Guidance on best available techniques and best environmental practices for the recycling and disposal of articles containing polybrominated diphenyl ethers (PBDEs) listed under the Stockholm Convention on Persistent Organic Pollutants


July 2012


The views expressed in this publication do not necessarily reflect the views of the Secretariat of the Stockholm Convention (SSC), the United Nations Environment Programme (UNEP), the United Nations Industrial Development Organization (UNIDO), the United Nations Institute for Training and Research (UNITAR), the United Nations (UN) or other contributory organizations. SSC, UNEP, UNIDO, UNITAR or the UN do not accept responsibility for the accuracy or completeness of the contents and shall not be liable for any loss or damage that may be occasioned, directly or indirectly, through the use of, or reliance on, the contents of this publication.

Table of Contents



1.2Structure of the guidance document10

1.3Relationship to the Basel Convention12

1.4Relationship to other environmental concerns12

2Background information on POP-PBDEs14

2.1POP-PBDEs listed in the Convention14

2.2Production of commercial PBDE mixtures15

2.3Former uses of POP-PBDEs15

2.3.1Former uses of c-PentaBDE15

2.3.2Former uses of c-OctaBDE16

2.4Risks associated with POP-PBDEs16

2.5POP-PBDEs in material/recycling flows and at end-of-life17

2.5.1C-PentaBDE in reuse, recycling and waste flows18

2.5.2C-OctaBDE in reuse, recycling and waste flows20

2.6Separation of POP-PBDEs-containing materials21

3General principles and cross-cutting considerations for the recycling and disposal of articles containing POP-PBDEs23

3.1General BAT/BEP considerations23

3.2Waste management23

3.2.1Producer responsibility24

3.3Life cycle management for POP-PBDE-containing materials25

3.3.1Life cycle considerations for the polymer fraction from vehicles25

3.3.2Life cycle considerations for recycling of WEEE and WEEE plastic26

3.3.3Life cycle considerations for the management of PUR foam26

3.3.4Life cycle considerations for bromine recovery26

3.4Alternatives to POP-PBDEs29

3.5Monitoring of POP-PBDEs/bromine in polymers31

4Specific BAT/BEP: POP-PBDE/BFR-containing plastic in WEEE32

4.1Reuse of EEE32

4.2Material recycling considerations for plastics containing POP-PBDEs32

4.2.1Labelling of POP-PBDE-containing plastic fractions and articles33

4.2.2Processing technologies for plastics to minimise exposure34

4.2.3Types and composition of POP-PBDE-containing plastics34

4.3Technologies to separate POP-PBDE-containing polymers36

4.3.1Manual dismantling approaches38

4.3.2Individual screening technologies to separate possibly POP-PBDE- containing bulk and shredded plastics39

4.3.3Combinations of technologies for producing marketable products41

4.3.4Comparison of technologies to separate polymer streams43

4.3.5Full-scale plants to separate WEEE and POP-PBDE-containing plastics44

4.4Energy recovery and end-of-life management of POP-PBDE plastics44

5Specific BAT/BEP: POP-PBDE/BFR materials in the transport sector45

5.1Reuse of vehicles containing POP-PBDEs46

5.2Treatment and recycling of end-of-life vehicles47

5.2.1Dismantling and depollution of the vehicle47

5.2.2Shredder plants48

5.2.3Recycling by improved depollution and post-shredding techniques49

5.3Energy recovery and disposal of ASR and other ELV residues50

5.3.1Energy recovery 50

5.3.2Disposal of ASR51

5.4Developing country considerations51

6Specific BAT/BEP: POP-PBDEs-containing PUR foam52

6.1Reuse of furniture and mattresses possibly impacted by POP-PBDEs52

6.2Recycling/recovery of PUR foam53

6.2.1Rebond: Recycling PUR foam with phase-out of c-PentaBDE53

6.2.2Material recovery from mattresses54


6.2.4Chemical recovery (glycolysis)54

6.3Labelling of articles produced from recycled PUR foams55

6.4Other materials possibly impacted by POP-PBDEs55

7Energy/material recovery from POP-PBDE-containing materials56

7.1General remarks on thermal treatment of POP-PBDE-containing materials56

7.1.1Calorific value and halogen content of POP-PBDE-containing materials56

7.1.2Monitoring of PBDD/PBDF and PXDD/PXDF release56

7.1.3Considerations on corrosion caused by bromine/HBr57

7.1.4Considerations for removal of HBr and bromine in flue gas treatments57

7.2Energy recovery of POP-PBDE-containing materials in incinerators57

7.2.1Co-incineration of plastics from WEEE58

7.2.2Co-incineration of ASR in municipal solid waste incinerators58

7.2.3Recovery of metals59

7.2.4Developing country considerations59

7.3Cement kilns59

7.3.1Developing country considerations61

7.4Melting systems61

7.5Pyrolysis and gasification of POP-PBDE-containing materials62

7.5.1Developing country considerations62

7.6Metal industries62

7.6.1Copper smelters and integrated smelters-refineries63

7.6.2Material recovery and energy recovery in electric arc furnaces65

7.6.3Feedstock recycling of POP-PBDE polymers in primary steel industry66

7.6.4POP-PBDE-containing materials in secondary aluminium industries67

7.6.5Antimony smelters recycling WEEE plastics67

7.6.6Developing/transition country considerations67

8Disposal of POP-PBDE-containing materials to landfills69

8.1Drawbacks of landfilling of POP-PBDE-containing materials69

8.2Sanitary landfill for disposal POP-PBDE-containing materials69

8.3Long-term aftercare considerations for sanitary landfills69



Annex 1: General BAT/BEP considerations82

Environmental management systems (EMS)82

Material/Waste management in facilities and processes83

Crushing, shredding, sieving and washing operations86

General BAT/BEP considerations in respect to air and water releases87

Prevention of soil contamination88

Annex 2: Generic BAT/BEP for processing technologies of plastic89

Techniques to reduce VOC/SVOC emission in process design89

Techniques to reduce VOC/SVOC emission in plant design89

Annex 3: Disposal of POP-PBDE-containing materials to landfills90

The landfilling of POP-PBDE-containing materials:90

Types of wastes containing POP-PBDEs that are landfilled91

Categories of landfills to receive POP-PBDE-containing wastes92

Delivery of wastes to landfills92

Operation and maintenance of landfills containing POP-PBDEs95

PBDE releases from landfills96

Release of POP-PBDEs from landfill fires97

BAT measures to prevent short- and long-term release of POP-PBDEs from landfills98

BAT/BEP of landfill after care100

Landfill mining and impact of POP-PBDEs100

Summary, conclusions and outlook about landfilling of POP-PBDE-containing materials with regard to BAT/BEP101

Annex 4: Recovery of bromine from POP-PBDE/BFR containing materials102

Thermal recovery of Bromine103

Technologies for separating POP-PBDEs/BFRs from the polymer matrix104

Annex 5. Determination of POP-PBDEs in articles106

Identification of POP-PBDEs by standard PBDE analysis106

Rapid GC-MS analysis techniques for POP-PBDEs106

In situ monitoring of PBDEs by Raman spectroscopy106

In situ measurement of bromine in articles107

Sliding spark spectroscopy107

X-ray fluorescence (XRF)107

X-ray transmission (XRT)107

List of Figures

Figure 11: Structure of the guidance and mass flow for the relevant production and application of c-PentaBDE and c-OctaBDE and the reuse, recycling and disposal of articles containing these substances12

Figure 31: Waste management hierarchy25

Figure 41: Composition of the polymer rich mixture after metal recovery from e-Waste shredding37

Figure 42: Polymer types identified in small WEEE polymer samples (%, w/w).38

Figure 43: Stepwise separation of polymers from waste of electrical and electronic equipment and their transformation into valuable plastic-for-recycling.40

Figure 51: Schematic of the processing of an end-of-life vehicle49

Figure 52: Overview of the shredder process51

Figure 53: Composition of shredder waste52

Figure A1 Potential options for the bromine recovery process and closing the bromine cycle (Tange and Drohmann 2002).108

List of Tables

Table 21: Typical PBDE homologue distribution in commercial PBDE products15

Table 22: Estimated total production of PBDE commercial mixtures, 1970-200516

Table 31: Comparative emissions and impacts of recycling and recovery technologies29

Table 41: Combinations of separation techniques, input materials, products, status of development and remarks on related economy46

Table 51: Parts that can be recycled from ELVs50

Table 52: Overview of post-shredder technologies53

Table 71: Redox potential of halogens and boiling/melting point of potassium and sodium halogenides60

Table 72: European Smelter Capacity68

Table A1: Types of landfills, and corresponding constraints for disposing of wastes containing POP-PBDEs. The table serves as an example based on existing classifications in Europe (European Commission 1999), and may vary in different countries99